CN105461925B - A kind of polyimides and its preparation method and application containing carbazole structure - Google Patents

A kind of polyimides and its preparation method and application containing carbazole structure Download PDF

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CN105461925B
CN105461925B CN201610003831.3A CN201610003831A CN105461925B CN 105461925 B CN105461925 B CN 105461925B CN 201610003831 A CN201610003831 A CN 201610003831A CN 105461925 B CN105461925 B CN 105461925B
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polyimides
polyimide material
containing carbazole
carbazole structure
preparation
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CN105461925A (en
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刘亦武
黄杰
谭井华
曾义
张海良
魏珊珊
刘跃军
向贤伟
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Hunan University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Disclosed by the invention is a kind of polyimides and its preparation method and application containing carbazole structure.Such polyimide material is used with aromatic diamines and various tetracid dianhydride of the high flatness containing carbazole structure as raw material, and the powder body material or film of polyimides are prepared by hot-imide or chemical imidization.Since the lowest energy state structure of wherein diamine monomer has high flatness and stronger rigidity, prepared polyimide molecule chain packing is close, and has excellent barrier property, higher glass transition temperature and thermal stability, lower coefficient of thermal expansion.The synthetic method craft of the present invention is simple, various, thus is suitable for industrial production.Polyimides disclosed in this invention can be widely applied to microelectronics, military project, aerospace, high-performance packaging and the new high-tech industries field such as protection and electron device package.

Description

A kind of polyimides and its preparation method and application containing carbazole structure
Technical field
The present invention relates to materials science fields, especially a kind of novel containing the polyimides of carbazole structure and its preparation side Method.
Technical background
Polyimides has excellent hot property, is industrialized at present due to containing imide ring on its main chain Best one of the kind of heat resistance in engineering plastics, with the incomparable comprehensive performance of other engineering plastics, such as machinery is strong Degree is high, resistant of high or low temperature is good, dielectricity is excellent, filming performance is good etc..PI is applied in every field, especially aobvious in flexibility Show, space flight and aviation, microelectronics and military industry field are widely used.
With the development of Flexible Displays industry, to PI, more stringent requirements are proposed.It usually requires that PI not only and to have and is excellent Hot property, also have excellent barrier property.By taking OLED device as an example, OLED device mainly wraps encapsulating material performance requirement It includes：1. hot property：300 DEG C of high temperature can be at least born, coefficient of thermal expansion is less than 20ppm/ DEG C；2. barrier property：Vapor Transmitance is less than 10-6g/m2·day；OTR oxygen transmission rate is less than 10-5cm3/m2·day；3. other aspects：Average surface roughness Less than 5nm；Chemical stability：It is acidproof, alkali, solvent；Film cannot be defective.General PI can meet surface roughness it is small, change Learn that stability is good and flawless requirement, most of PI can meet performance requirements, but can meet simultaneously currently without PI The requirement of hot property and barrier property.Therefore, polyimides of the exploitation with excellent thermal and barrier property is with important meaning Justice.
Polyimides has excellent hot property, therefore it is the key that research to improve its barrier property.Improve polyimides There are mainly three types of the approach of barrier property：(1) the Intrinsical polyimides of synthesizing new structure；(2) polyimide nano is prepared Composite material；(3) physical method is used to be modified, such as magnetron sputtering, LBL self-assembly.But by preparing nanocomposite to material Expect that the improvement dynamics of barrier property is little, physical method, which is modified, needs expensive equipment, and complex process；And fundamentally It says, second method and the third method are based on first method, i.e. the high a kind of new structural Intrinsical of synthesis is high Polyimides is obstructed, can be prepared more by the methods of nano combined or magnetron sputtering based on this Intrinsical polyimides The polyimide material of high obstructing performance.Therefore, the Intrinsical high-barrier polyimides of synthesizing new structure is to solve the problems, such as At all.The barrier property and hot property of polymer can be improved by introducing planar structure, hydrogen bond etc. in the polymer backbone.Such as patent US5134218, US5464924, US5962621-A introduce some planar structures in the polymer backbone, hydrogen bond is prepared for high resistant Every novel Intrinsical polymer.For another example patent CN200610010286.7 planar structures such as Yin Ru oxazoles in polyimides main chain It is prepared for the novel Intrinsical polymer of high thermal stability.But planar structure is introduced into pendant manner in polymer chain and is then reached Less than the effect for improving polymer barrier performance, its dissolubility (such as 102352039 A, CN of patent CN can only be changed 102766085 A etc.).However, when proposing requirements at the higher level to material thermal resistance with certain high-barrier fields, at present for simultaneously The research of polyimide material with excellent thermal and high obstructing performance or less, it is therefore necessary to carry out excellent hot Study on the synthesis can be designed with the polyimides of high obstructing performance.
Invention content
The object of the present invention is to provide a kind of novel polyimides containing carbazole structure.
Another object of the present invention is to provide the preparation methods of the above-mentioned polyimides containing carbazole structure.
The object of the present invention is achieved like this：A kind of novel polyimides containing carbazole structure, general structure are：
Wherein：N is one or more of 1~10000, the Y in following general structure：
Wherein Ar1Selected from any one of following structural：
- C ≡ CH ,-NO2,-CHO ,-OH ,-COOH ,-SO3H ,-F ,-Cl ,-Br ,-I,(wherein X1, X2, X3, X4, X5- CH=CH can be selected from2,-C ≡ CH ,-NO2,-CHO ,- OH ,-COOH ,-SO3Arbitrary structures in H ,-F ,-Cl ,-Br ,-I).
Wherein Ar2Selected from any one of following structural：
- H ,-CH3,-CH=CH2,-C ≡ CH ,-CHO ,-OH ,-COOH ,-SO3H ,-F ,-Cl ,-Br ,- I,(wherein X6, X7, X8, X9, X10- CH can be selected from3,-CH=CH2,-C ≡ CH ,-CHO ,- OH ,-COOH ,-SO3Arbitrary structures in H ,-F ,-Cl ,-Br ,-I).
Wherein, Ar3Selected from any one of following structural：
N=0~6, m=0~6, p=0~6, n, m in same structure formula be 0 when p differences.
Wherein, Ar4Selected from any one of following structural：
It is 0 when a=1~6, b=0~6, n=0~6, b and n difference.
And Ar3、Ar4In Ar5And Ar6Selected from any one of following structural：
And Ar3In Ar7Selected from any one of following structural：
One or more of the X in following general structure：
Another object of the present invention is to provide the preparation method of the above-mentioned polyimides containing carbazole structure, and this method is：Argon It is 1 in molar ratio by the diamines containing Y structure and the dianhydride containing X architecture in gas atmosphere:(0.9~1.1) is dissolved in N- crassitudes Ketone, dimethyl sulfoxide (DMSO), dimethyl sulfone, sulfolane, Isosorbide-5-Nitrae-dioxane, n,N-dimethylacetamide, n,N-Dimethylformamide, In one or more kinds of highly polar aprotic organic solvents of mixing in metacresol, tetrahydrofuran, diamines containing Y structure with Dianhydride gross mass containing X architecture accounts for the 2~50% of reaction mass gross mass, is stirred to react 0.5~72h at -10~40 DEG C, obtains Homogeneously, sticky polyamic acid glue, and polyamic acid glue is dehydrated by hot-imide or chemical imidization Obtain polyimide material.
The concrete operation step of the hot-imide method is：On a glass by polyamic acid glue blade coating, then by glass Glass plate is placed in vacuum drying oven, is vacuumized, and temperature program is：Room temperature to constant temperature whole process after 100 DEG C 0.8~3 hour, From 100 DEG C be warming up to 200 DEG C after constant temperature whole process 0.8~2 hour, 300 DEG C of constant temperature whole process 0.8 are warming up to from 200 DEG C ~2 hours, from 300 DEG C be warming up to 350 DEG C~500 DEG C after constant temperature whole process 0.5~2 hour, polyamides Asia is can be taken off after cooling Amine film.
The concrete operation step of the chemical imidization method is：In polyamic acid glue be added pyridine/acetic anhydride or Triethylamine/acetic anhydride or sodium acetate/acetic anhydride are as dehydrating agent, heating stirring, be heated to 60~170 DEG C continue stirring 0.5~ 6h is poured into methanol or acetone after being cooled to room temperature and is obtained polyimides precipitation, filtration drying to get to polyimides powder, If you need to prepare membrane material, then polyimides powder can be dissolved in N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO), N, In N- dimethylacetylamides (DMAc), n,N-Dimethylformamide (DMF), metacresol (m-Cresol) or tetrahydrofuran (THF), It is heated to after being completely dissolved, on a glass by polyimide solution blade coating, 70~200 DEG C of vacuum drying removal solvents are cooling After can be taken off polyimide film.
The preparation method of the polyimides containing carbazole structure proposed is invented, preparation process is simple and various, and condition is wanted It asks low, thus is suitable for industrial production.Since diamine monomer therein has high flatness and stronger rigidity, prepared polyamides Imines molecule chain packing is close, thus has excellent barrier property, higher glass transition temperature and thermal stability, relatively low Coefficient of thermal expansion.Such polyimides containing carbazole structure can be used for microelectronics, military project, aerospace, high-performance packaging with The new high-tech industries field such as protection and electron device package.
Description of the drawings
Fig. 1 is the infrared spectrogram of Examples 1 to 7 resulting polymers, wherein：
A corresponds to 9-M-CNPDA/PMDA-PI
B corresponds to CAPDA/PMDA-PI
C corresponds to CEPDA/PMDA-PI
D corresponds to CESPDA/PMDA-PI
E corresponds to 9-Ph-CDA/PMDA-PI
F corresponds to 9-Ph-CDA/PMDA-PI
G corresponds to 2,7-CPDA/PMDA-PI
It can see from infrared spectrogram, in 1780 and 1720cm-1It is nearby the asymmetric and right of carbonyl on imide ring Claim stretching vibration, 725cm-1It is nearby the bending vibration of carbonyl on imide ring, 1380cm-1It is nearby that the flexible of imide ring shakes It is dynamic.1621cm in a-1There is the characteristic absorption peak of stronger-OH in place；1623cm in b-1There is the bending vibration of stronger N-H in place Absorption peak；1780cm in c-1There is the characteristic absorption peak of stronger C=O in place；1015cm in d-1There are C-O-C characteristic absorptions in place Peak；Since conjugation makes C=O characteristic absorption peaks move to 1650cm in e and f-1Near, these all illustrate that Examples 1 to 7 has all succeeded Synthesis.
Specific implementation mode
Example is given below so that the present invention will be described in more detail, it is necessary to be pointed out that following embodiment cannot be explained For the limitation to invention protection domain, the person skilled in the art in the field present invention is made according to foregoing invention content some Nonessential modifications and adaptations should belong to the scope of protection of the present invention.
Embodiment 1
At room temperature, by 3.9348g (0.01mol) N1, N1'- (9-methyl-9H-carbazole-3,6-diyl) bis- (benzene-1,4-diamine) (9-M-CNPDA) and 57.3g (60.7ml) N,N-dimethylformamide is added to 100ml's In three-necked flask, it is passed through argon gas, is stirred, after being completely dissolved, 2.1812g (0.01mol) 1,2,4,5- is added Benzenetetracarboxylic anhydride (1,2,4,5- pyromellitic acid anhydride, PMDA), continue to be stirred to react 6h, Obtain the sticky polyamic acid solution of homogeneous phase transparent.It will be scratched on a glass after polyamic acid solution bubble removing again, then by glass Glass plate is placed in vacuum drying oven, is vacuumized, and temperature program is：Room temperature to constant temperature whole process 1h → 100 DEG C after 100 DEG C rise Temperature to constant temperature whole process 1h → 200 DEG C after 200 DEG C are warming up to after 300 DEG C of constant temperature whole process 1h~300 DEG C are warming up to 400 DEG C Constant temperature whole process 1h can be taken off polyimide film after cooling.In the infrared spectrogram of polyimide film such as annex one shown in a.
The molecular structural formula of aroma type function polyimides (9-M-CNPDA/PMDA-PI) film in the present embodiment is such as Under：
Embodiment 2
At room temperature, by 4.3548g (0.01mol) N3, N6-bis (4-aminophenyl) -9H-carbazole-3,6- Dicarbo-xamide (CAPDA) and 51.1g (58.4ml) n,N-Dimethylformamide are added into the three-necked flask of 100ml, It is passed through argon gas, is stirred, after being completely dissolved, 2.1812g (0.01mol) 1,2,4,5-Benzenetetracarboxylic is added Anhydride (1,2,4,5- pyromellitic acid anhydride, PMDA) continues to be stirred to react 6h, obtains the sticky polyamides of homogeneous phase transparent Amino acid solution.It will be scratched on a glass after polyamic acid solution bubble removing again, then glass plate be placed in vacuum drying oven, taken out true Sky, temperature program are：Constant temperature whole process after room temperature is warming up to 200 DEG C to constant temperature whole process 1h → 100 DEG C after 100 DEG C 1h → 200 DEG C are warming up to constant temperature whole process 1h after 300 DEG C of constant temperature whole process 1h~300 DEG C are warming up to 400 DEG C, can after cooling Take out polyimide film.In the infrared spectrogram of polyimide film such as annex one shown in b.
The molecular structural formula of aroma type function polyimides (CAPDA/PMDA-PI) film in the present embodiment is as follows：
Embodiment 3
At room temperature, by 3.8148g (0.01mol) 4,4'- ((9H-carbazole-3,6-diyl) bis (oxy)) Dianiline (CEPDA) and 63.9g (67.7ml) n,N-Dimethylformamide are added into the three-necked flask of 100ml, are passed through argon After being completely dissolved, 2.1812g (0.01mol) 1,2,4,5-Benzenetetracarboxylic is added in gas, stirring Anhydride (1,2,4,5- pyromellitic acid anhydride, PMDA) continues to be stirred to react 6h, obtains the sticky polyamides of homogeneous phase transparent Amino acid solution.It will be scratched on a glass after polyamic acid solution bubble removing again, then glass plate be placed in vacuum drying oven, taken out true Sky, temperature program are：Constant temperature whole process after room temperature is warming up to 200 DEG C to constant temperature whole process 1h → 100 DEG C after 100 DEG C 1h → 200 DEG C are warming up to constant temperature whole process 1h after 300 DEG C of constant temperature whole process 1h~300 DEG C are warming up to 400 DEG C, can after cooling Take out polyimide film.In the infrared spectrogram of polyimide film such as annex one shown in c.
The molecular structural formula of aroma type function polyimides (CEPDA/PMDA-PI) film in the present embodiment is as follows：
Embodiment 4
At room temperature, by 4.3745g (0.01mol) bis (4-aminophenyl) 9H-carbazole-3,6- Dicarboxylate (CESPDA) and 61.8g (65.5ml) n,N-Dimethylformamide are added into the three-necked flask of 100ml, It is passed through argon gas, is stirred, after being completely dissolved, 2.1812g (0.01mol) 1,2,4,5-Benzenetetracarboxylic is added Anhydride (1,2,4,5- pyromellitic acid anhydride, PMDA) continues to be stirred to react 6h, obtains the sticky polyamides of homogeneous phase transparent Amino acid solution.It will be scratched on a glass after polyamic acid solution bubble removing again, then glass plate be placed in vacuum drying oven, taken out true Sky, temperature program are：Constant temperature whole process after room temperature is warming up to 200 DEG C to constant temperature whole process 1h → 100 DEG C after 100 DEG C 1h → 200 DEG C are warming up to constant temperature whole process 1h after 300 DEG C of constant temperature whole process 1h~300 DEG C are warming up to 400 DEG C, can after cooling Take out polyimide film.In the infrared spectrogram of polyimide film such as annex one shown in d.
The molecular structural formula of aroma type function polyimides (CESPDA/PMDA-PI) film in the present embodiment is as follows：
Embodiment 5
At room temperature, by 2.8933g (0.01mol) 4- (3,6-diamino-9H-carbazol-9-yl) phenol (9-Ph- CDA it) is added into the three-necked flask of 100ml with 61.8g (65.5ml) n,N-Dimethylformamide, is passed through argon gas, stirred, completely After dissolving, 2.1812g (0.01mol) 1,2,4,5-Benzenetetracarboxylic anhydride (1,2,4,5- is added Pyromellitic acid anhydride, PMDA), continue to be stirred to react 6h, obtains the sticky polyamic acid solution of homogeneous phase transparent.Again by polyamide It scratches on a glass, then glass plate is placed in vacuum drying oven, vacuumizes after acid solution bubble removing, temperature program is：Room temperature Constant temperature whole process 1h → 200 DEG C are warming up to 300 after constant temperature whole process 1h → 100 DEG C are warming up to 200 DEG C after being warming up to 100 DEG C Constant temperature whole process 1h after DEG C constant temperature whole process 1h~300 DEG C are warming up to 400 DEG C can be taken off polyimide film after cooling.It is poly- In the infrared spectrogram of acid imide film such as annex one shown in e.
The molecular structural formula of aroma type function polyimides (9-Ph-CDA/PMDA-PI) film in the present embodiment is as follows：
Embodiment 6
Polyamic acid solution is prepared in 5 identical method of embodiment, polyimides is then prepared using chemical imidization, Step is such as：5mL acetic anhydrides are added in gained polyamic acid solution, continues to stir, is slow added into 2.5mL triethylamines, and rise Temperature continues solution blade coating after stirring 6h and is placed in vacuum drying oven on cleaned glass plate, then by glass plate, vacuumized to 70 DEG C, 100 DEG C of dry 12h can be taken off polyimide film after cooling.In the infrared spectrogram of polyimide film such as annex one shown in f.
Embodiment 7
At room temperature, by 3.4943g (0.01mol) 4,4'- (9H-carbazole-2,7-diyl) dianiline (2,7- CPDA it) is added into the three-necked flask of 100ml with 61.8g (65.5ml) n,N-Dimethylformamide, is passed through argon gas, stirred, it is complete After fully dissolved, addition 2.1812g (0.01mol) 1,2,4,5-Benzenetetracarboxylic anhydride (1,2,4, 5- pyromellitic acid anhydrides, PMDA), continue to be stirred to react 6h, obtains the sticky polyamic acid solution of homogeneous phase transparent.Again by polyamides It is scratched on a glass after amino acid solutions bubble, then glass plate is placed in vacuum drying oven, vacuumized, temperature program is：Room Constant temperature whole process 1h → 200 DEG C are warming up to after constant temperature whole process 1h → 100 DEG C are warming up to 200 DEG C after temperature is warming up to 100 DEG C Constant temperature whole process 1h after 300 DEG C of constant temperature whole process 1h~300 DEG C are warming up to 400 DEG C can be taken off polyimide film after cooling. In the infrared spectrogram of polyimide film such as annex one shown in g.
The molecular structural formula of aroma type function polyimides (2,7-CPDA/PMDA-PI) film in the present embodiment is as follows：

Claims (9)

1. a kind of polyimide material containing carbazole structure, general formula of molecular structure are as follows：
Wherein：N is one or more of 1~10000, the Y in following general structure：
Wherein Ar1Selected from any one of following structural：
- C ≡ CH ,-NO2,-CHO ,-OH ,-COOH ,-SO3H ,-F ,-Cl ,-Br ,-I；
Wherein Ar2Selected from any one of following structural：
- H ,-CH3,-CH=CH2,-C ≡ CH ,-CHO ,-OH ,-COOH ,-SO3H ,-F ,-Cl ,-Br ,-I；
Wherein, Ar3Selected from any one of following structural：
N=0~6, m=0~6, p=0~6, n, m in same structure formula be 0 when p differences；
Wherein, Ar4Selected from any one of following structural：
It is 0 when a=1~6, b=0~6, n=0~6, b and n difference；
And Ar3、Ar4In Ar5And Ar6Selected from any one of following structural：
And Ar3In Ar7Selected from any one of following structural：
One or more of the X in following general structure：
2. the polyimide material containing carbazole structure according to claim 1, it is characterised in that：Polyimide material can be made For at powder, film.
3. the preparation method of the polyimide material containing carbazole structure according to claim 1, it is characterised in that：Argon gas atmosphere In, it is 1 in molar ratio by the diamines containing Y structure and the dianhydride containing X architecture:(0.9~1.1) is dissolved in highly polar non-proton organic molten In agent, it is stirred to react 0.5~72h at -10~40 DEG C, obtains homogeneous, sticky polyamic acid glue, and to polyamic acid glue It is dehydrated to obtain polyimide material.
4. the preparation method of the polyimide material containing carbazole structure according to claim 3, it is characterised in that：Containing Y structure Diamines and the dianhydride gross mass containing X architecture account for the 2~50% of reaction mass gross mass.
5. the preparation method of the polyimide material containing carbazole structure according to claim 3, it is characterised in that：It is highly polar non- Proton-organic solvent is N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), dimethyl sulfone, sulfolane, Isosorbide-5-Nitrae-dioxane, N, N- diformazans One or more kinds of mixtures in yl acetamide, n,N-Dimethylformamide, metacresol, tetrahydrofuran.
6. the preparation method of the polyimide material containing carbazole structure according to claim 3, it is characterised in that：Polyamic acid The method that glue is dehydrated to obtain polyimides can be hot-imide or chemical imidization.
7. the preparation method of the polyimide material containing carbazole structure according to claim 6, it is characterised in that：Hot acid imide The concrete operations of change are：Polyamic acid glue blade coating on a glass, then by glass plate is placed in vacuum drying oven, is vacuumized, Temperature program is：Room temperature to constant temperature whole process after 100 DEG C 0.8~3 hour, from 100 DEG C be warming up to 200 DEG C after constant temperature it is whole A process 0.8~2 hour, 300 DEG C of constant temperature whole process is warming up to from 200 DEG C 0.8~2 hour, and 350 DEG C are warming up to from 300 DEG C Constant temperature whole process 0.5~2 hour after~500 DEG C can be taken off polyimide film after cooling.
8. the preparation method of the polyimide material containing carbazole structure according to claim 6, it is characterised in that：Chemical acyl is sub- The concrete operations of amination are：Pyridine/acetic anhydride or triethylamine/acetic anhydride or sodium acetate/second are added in polyamic acid glue As dehydrating agent, heating stirring is heated to 60~170 DEG C and continues 0.5~6h of stirring acid anhydrides, poured into after being cooled to room temperature methanol or Polyimides precipitation is obtained in acetone, filtration drying, then can be by polyamides if you need to prepare membrane material to get to polyimides powder Imines powder is dissolved in N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO), n,N-dimethylacetamide (DMAc), N, N- It in dimethylformamide (DMF), metacresol (m-Cresol) or tetrahydrofuran (THF), is heated to after being completely dissolved, by polyamides Asia Amine aqueous solution scratches on a glass, and 70~200 DEG C of vacuum drying removal solvents can be taken off polyimide film after cooling.
9. the polyimide material according to claim 1 containing carbazole structure, it is characterised in that its can be applied to microelectronics, Military project, aerospace, high-performance packaging and protection and electron device package new high-tech industry field.
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